Electronically Driven Stereogenesis

有机动力学项目将支持纽约州立大学石溪分校化学系William J. le Noble教授对“电子驱动立体生成”的研究。他将探索三角形碳的键形成和四角形碳的键解理的原理，在反周面位置上具有最富电子的sigma键的那一侧的面选择性更有利。在这个项目中，le Noble教授正在进行三个主要领域的研究，将利用2,5-二取代金刚烷的独特优势作为探针来研究非对映面选择中的立体电子效应。研究的一个领域将涉及检查一个简单规则的范围，根据该规则，键的形成（加成反应）：三角碳上的亲电加成、亲核加成、周环反应等，以及四角形碳上的键解理（脱羧、碎裂、溶剂溶解等）都发生在反周面键富电子最多的面。金刚烷骨架的刚性保证了在构象不确定性中没有旋转运动将掩盖观察到的面选择。另一个研究领域涉及手性转移，第三个领域涉及2-和5-甲酰基金刚烷的溶剂溶解动力学研究。

The Organic Dynamics Program will support Professor William J. le Noble's study of "Electronically Driven Stereogenesis" in the Chemistry Department at the State University of New York at Stony Brook. He will explore the principle that bond formation at trigonal carbon and bond cleavage at tetragonal carbon are favored in face selectivity on that side which has the most electron-rich sigma bond in the antiperiplanar position. In this project, Professor le Noble is pursuing three major areas of research that will exploit unique advantages of 2,5-disubstituted adamantanes as probes to study stereoelectronic effects in diastereofacial selection. One area of study will involve examination of the scope of a simple rule according to which bond formation (addition reactions: electrophilic addition, nucleophilic addition, pericyclic reactions, etc.) at trigonal carbon and bond cleavage (decarboxylation, fragmentation, solvolysis, etc.) at tetragonal carbon occur at that face which has the most electron rich bond antiperiplanar. The rigidity of the adamantane skeleton guarantees that no rotational motion will shroud the observed face selection in conformational uncertainty. Another area of study deals with the transfer of chirality, and the third area deals with the kinetic studies of solvolysis of 2- and 5-tosyl adamantanes.